CN104752706B - Lithium ion battery cathode active material and preparation method, lithium ion battery cathode material, lithium ion battery cathode as well as lithium ion battery - Google Patents
Lithium ion battery cathode active material and preparation method, lithium ion battery cathode material, lithium ion battery cathode as well as lithium ion battery Download PDFInfo
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- CN104752706B CN104752706B CN201310752847.0A CN201310752847A CN104752706B CN 104752706 B CN104752706 B CN 104752706B CN 201310752847 A CN201310752847 A CN 201310752847A CN 104752706 B CN104752706 B CN 104752706B
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- lithium ion
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- ion battery
- hectorite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery cathode active material and a preparation method, a lithium ion battery cathode material, a lithium ion battery cathode as well as a lithium ion battery. The cathode active material disclosed by the invention contains intercalation modified hectorite and GeO2, wherein at least part of an intercalation agent of the intercalation modified hectorite comes from GeO2, and the layer spacing d001 of the intercalation modified hectorite is 1.2-5 nm. Compared with a lithium ion battery only adopting the GeO2 as the cathode active material, the lithium ion battery adopting the cathode active material disclosed by the invention shows high reversible capacity, good cycling performance and excellent high rate performance.
Description
Technical field
The present invention relates to a kind of lithium ion battery anode active material and preparation method and formed by this negative active core-shell material
Negative material, the invention still further relates to a kind of lithium ion battery negative and a kind of lithium ion battery.
Background technology
Lithium ion battery has that operating voltage height, light weight, self discharge be little and the outstanding advantages such as non-environmental-pollution due to it,
Become the ideal source of the electronic installation miniaturization such as video camera, mobile phone, be also future automobile high-energy power battery
First-selected power supply.
Negative material is one of critical material of lithium ion battery.At present, the most frequently used lithium ion battery negative material is
Graphite negative electrodes material.Graphitic conductive is good, and degree of crystallinity is high, has good layer structure, is more suitable for the embedded, de- of li ion
Go out, and there are wide material sources and cheap, therefore, the negative pole material of most lithium ion batteries commercially
Expect for graphite-like.However, the lamellar structure of graphite leads to its tap density ratio relatively low, typically in 0.6g/cm3Hereinafter, it is difficult to completely
The requirement of the high energy density per unit volume of sufficient lithium ion battery, simultaneously poor with solvent compatibility, being total to because of solvent molecule during first charge-discharge
Embedded make that graphite linings are peeling-off to lead to electrode life to be reduced.Shake although graphite being carried out with spheroidization and can improving native graphite
Real density and modification can improve its reversible capacity and cycle life, but this technique is more complicated.
Except graphite negative electrodes material, also other lithium ion battery negative materials, such as tin-based material, silica-base material,
Transition metal oxide, lithium alloy and nano-electrode material etc., but also there are some yet unresolved issues in these materials.As mistake
When crossing metal oxide materials as negative material, lithium ion battery can be made to have the theoretical specific capacity more than 700mah/g；Cross
Cross metal oxide materials as ion cathode material lithium reaction mechanism be distinct from the embedding de- lithium reaction of graphite material or sn,
The alloying reaction of si class material, but a kind of reversible redox reaction, the application prospect tentatively showing.But transition
The conductance of metal oxide is low, and in charge and discharge process, the Volume Changes of material are big, cause lithium ion battery high rate performance and
Stable circulation performance is poor；Meanwhile, the irreversible capacity loss that solid electrolyte interface (sei) film of formation causes is larger,
Reduce the generation that scantling can promote material surface side reaction further, lead to larger irreversible capacity, and shorten use
Life-span.
Germanium (ge) negative material with its higher capacity, higher lithium ion diffusion coefficient, preferable electric conductivity, relatively low
The advantage such as lithium current potential and abundant earth's crust reserves is attracted attention.At present, germanium dioxide (geo2) and its multiple
Compound with its stability and easier synthetic method, become can business application a kind of lithium ion battery negative material.
Content of the invention
Find in research process, use geo2There is asking of cycle performance difference in the lithium ion battery as negative active core-shell material
Topic.Find through research, using geo2As negative active core-shell material lithium ion battery cycle performance difference the reason be probably:
In the charge and discharge process of battery, the embedded and abjection of lithium ion can cause geo2The violent Volume Changes of particle, when maximum
Up to 120-200%, this violent Volume Changes may result in geo to this Volume Changes2Negative material is lost and collector
Electrical contact, leads to its capacity rapid decrease.
In order to solve to adopt geo2The above-mentioned technical problem existing as the lithium ion battery of negative active core-shell material, the present invention
Inventor conduct in-depth research, find: by geo2It is combined with hectorite, make at least part of geo2It is intercalation into hectorite
Interlayer, the Volume Changes that can be caused due to the embedded of lithium ion and abjection in buffer battery charge and discharge process, can also simultaneously
Guarantee geo2Particle has good electron conduction, and thus the lithium ion battery as negative active core-shell material preparation shows height
Reversible capacity, good cycle performance and excellent high rate capability.Complete the present invention on this basis.
According to the first aspect of the invention, the invention provides a kind of lithium ion battery anode active material, this negative pole
Active material contains intercalation modifying hectorite and geo2, wherein, the intercalator of described intercalation modifying hectorite at least partially from
In described geo2, interlamellar spacing d of described intercalation modifying hectorite001For 1.2-5nm.
According to the second aspect of the invention, the invention provides a kind of preparation side of lithium ion battery anode active material
Method, the method includes: under the conditions of hydrolysis, at least one compound is contacted with the aqueous dispersions containing hectorite, institute
State compound and can form geo under the conditions of hydrolysis2.
According to the third aspect of the present invention, the invention provides the lithium ion battery negative prepared by said method is active
Material.
According to the fourth aspect of the present invention, the invention provides a kind of lithium ion battery negative material, this negative material
Including negative active core-shell material and adhesive, wherein, the negative active core-shell material that described negative active core-shell material provides for the present invention.
According to the fifth aspect of the present invention, the invention provides a kind of lithium ion battery negative, this negative pole includes current collection
Body and coating and/or be filled in negative material on collector, wherein, the negative pole material that described negative material provides for the present invention
Material.
According to the sixth aspect of the invention, the invention provides a kind of lithium ion battery, this battery includes pole piece and non-
Water electrolysis liquid, described pole piece and nonaqueous electrolytic solution are sealed in battery container, and described pole piece includes positive pole, negative pole and barrier film, its
In, the negative pole that described negative pole provides for the present invention.
With only with geo2Lithium ion battery as negative active core-shell material is compared, using the negative active core-shell material of the present invention
Lithium ion battery show high reversible capacity, good cycle performance and excellent circulation performance.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of specification, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the xrd figure of the negative active core-shell material according to the present invention, and wherein, curve a corresponds to former as embodiment 1
The hectorite of material, curve b corresponds to the negative active core-shell material of embodiment 1 preparation, and curve c corresponds to the use table in embodiment 2
The modified hectorite of face activating agent, curve d corresponds to the negative active core-shell material of embodiment 2 preparation.
Fig. 2 is the circulation performance chart of lithium ion battery c1.
Fig. 3 is the circulation performance chart of lithium ion battery c2.
Fig. 4 is the circulation performance chart of lithium ion battery d1.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
According to the first aspect of the invention, the invention provides a kind of lithium ion battery anode active material, this negative pole
Active material contains intercalation modifying hectorite and geo2, wherein, the intercalator of described intercalation modifying hectorite at least partially from
In described geo2, interlamellar spacing d of described intercalation modifying hectorite001For 1.2-5nm.The interlayer of described intercalation modifying hectorite by
In having intercalator, therefore compared with raw material hectorite, interlamellar spacing increases.According in the negative active core-shell material of the present invention, described
Interlamellar spacing d of intercalation modifying hectorite001For 1.2-5nm, it can be generally interlamellar spacing d of the hectorite as raw material001's
1.2-10 again.Preferably, interlamellar spacing d of described intercalation modifying hectorite001For 1.9-3.5nm, it is the hectorite as raw material
Interlamellar spacing d0011.5-7 times.In the present invention, using x-ray diffraction method, hectorite is analyzed, and according to Prague
(bragg) equation calculates interlamellar spacing d of hectorite001.
Described intercalation modifying hectorite and geo2Mass ratio with can either make hectorite keep layer structure, can make again
The lithium ion battery that must finally prepare has good cycle performance and is defined.Preferably, with li2The described intercalation modifying lithium of o meter
Saponite and geo2Mass ratio be 1:2.4-9.5.It is highly preferred that with li2The described intercalation modifying hectorite of o meter and geo2Matter
Amount ratio is 1:4-8.In the present invention, using li in x-ray fluorescence spectrometry negative active core-shell material2O and geo2Content.
From the angle of the cycle performance improving the lithium ion battery being made up of described negative active core-shell material further, excellent
In the case of choosing, described negative active core-shell material also contains at least one cationic surfactant, described intercalation modifying hectorite
Intercalator part comes from described cationic surfactant.Cationic surfactant energy is introduced by the interlayer in hectorite
Enough interlamellar spacings increasing intercalation modifying hectorite further, and can also be right by the content adjusting cationic surfactant
The interlamellar spacing of intercalation modifying hectorite is adjusted.Also contain at least one cation surface activating in described negative active core-shell material
During agent, the interlamellar spacing of described intercalation modifying hectorite is generally d001For more than 1.5nm, preferably more than 2.5nm.
According to the negative active core-shell material of the present invention, the content of described cationic surfactant is to enable to intercalation modifying
The interlamellar spacing of hectorite disclosure satisfy that above-mentioned requirements are defined.Usually, on the basis of the gross mass of described negative active core-shell material, institute
The content stating cationic surfactant is 0.01-1 weight %, preferably 0.01-0.5 weight %.In the present invention, negative electrode active
The content of material cationic surfactant is calculated according to thermogravimetic analysis (TGA).
Described cationic surfactant can for common various can swap with the cation of hectorite interlayer,
Cationic surfactant hence into the interlayer of hectorite.Specifically, described cationic surface active agent can be ten
Six alkyl trimethyl ammonium bromides (ctab), dodecyl benzyl dimethyl ammonium chloride, double octyl ditallowdimethyl ammonium bromide and Buddha's warrior attendant
One or more of alkane mono-quaternaries, preferably cetyl trimethylammonium bromide.
According to the second aspect of the invention, the invention provides a kind of preparation side of lithium ion battery anode active material
Method, the method includes: under the conditions of hydrolysis, at least one compound is contacted with the aqueous dispersions containing hectorite, institute
State compound and can form geo under the conditions of hydrolysis2.
The present invention is not particularly limited for the hectorite as raw material, can be the hectorite in common various sources,
For example, described hectorite can be natural hectorite and/or artificial synthesized hectorite.The method of LAPONITE is this area
Known, no longer describe in detail herein.
The preparation method of described aqueous dispersions is not particularly limited.Usually, can by hectorite is mixed with water and
Obtain.From the angle improving dispersion effect in water for the hectorite further, described mixing can be 60-80 DEG C in temperature
Under conditions of carry out.The time of described mixing is defined by being mixed hectorite with water, can be typically 2-4h.Described
In aqueous dispersions, the concentration of hectorite can be typically 3-6 weight %.Described mixing various can have stirring dress common
Carry out in the blender put.
The method according to the invention, in a preferred embodiment, the method obtaining described aqueous dispersions includes: will
Hectorite and water are mixed to get mixture, more described mixture is contacted with least one cationic surfactant, so that extremely
Small part cationic surfactant enters the interlayer of described hectorite.So can effectively increase the interlamellar spacing of hectorite,
Thus being conducive to the follow-up interlayer in hectorite to introduce geo2.
The consumption of described cationic surfactant is defined by the interlamellar spacing that can effectively increase hectorite.Usually,
The consumption of cationic surfactant should increase the interlamellar spacing of hectorite, makes geo2Particle enters lithium soap as much as possible
The interlayer of stone, but geo will not be far longer than due to the interlamellar spacing of hectorite again2The particle size of particle, and lead to enter lithium
The geo of saponite interlayer2Particle detaches the interlayer of hectorite again.In the present invention, the consumption of described cationic surfactant
So that in the negative active core-shell material of final preparation, the content of cationic surfactant is 0.01-1 weight %, preferably 0.01-
0.5 weight %.
The condition that described mixture is contacted with described cationic surfactant is to enable to cation surface activating
Agent is exchanged with the cation of hectorite interlayer, and the interlayer entering hectorite is defined.Usually, can be in 60-80 DEG C of temperature
Under degree, described mixture is contacted with described cationic surfactant.Described mixture is connect with described cationic surfactant
The tactile time is defined by the interlayer that enough cationic surfactants can be made to enter hectorite, can be typically 0.5-1.5
Hour.
Described cationic surfactant can for common various can swap with the cation of hectorite interlayer,
Cationic surfactant hence into the interlayer of hectorite.Specifically, described cationic surfactant can be 16
Alkyl trimethyl ammonium bromide, dodecyl benzyl dimethyl ammonium chloride, double octyl ditallowdimethyl ammonium bromide and adamantane single cropping ammonium
One or more of salt, preferably cetyl trimethylammonium bromide.
The method according to the invention, can form geo by making at least one under the conditions of hydrolysis2Compound with
Described aqueous dispersions contact under the conditions of hydrolysis, thus the interlayer in hectorite introduces geo2.
Described compound various can form geo for common under the conditions of hydrolysis2Material.For example, institute
Stating compound can be gex4, x can be cl or br.
The consumption of described compound can be selected according to the composition of expected negative active core-shell material.Usually, described
The consumption of compound makes in the negative active core-shell material finally prepared with li2The described intercalation modifying hectorite of o meter and geo2Matter
Amount ratio is 1:2.4-9.5, preferably 1:4-8.The use of described compound is determined by the composition of expected negative active core-shell material
The method of amount is the experiment that those skilled in the art pass through limited number of time is confirmable, no longer describes in detail herein.
In a preferred embodiment, before described aqueous dispersions are contacted with described compound, the side of the present invention
Method also includes for the ph value of described aqueous dispersions being adjusted to 10-11.
Using conventional various methods, the ph value of described aqueous dispersions can be adjusted to be within above range.Specifically
Ground, can pass through to add at least one water-soluble alkaline compound in described aqueous dispersions, so that described aqueous dispersions
Ph value is within above range.Described water-soluble alkaline compound can be nh3And/or m (oh)n, n is the chemical valence phase with m
Same integer, m can be typically alkali metal or alkaline-earth metal.Specifically, described water-soluble alkaline compound can be but not limit
In: nh3, NaOH, at least one in sodium carbonate and potassium hydroxide, preferably NaOH.For nh3, preferably with water-soluble
Liquid form uses, that is, using ammoniacal liquor.The consumption of described water-soluble alkaline compound is can adjust the ph value of described aqueous dispersions
Save and be defined for being within above range.
Described hydrolysis condition forms geo can make described compound2It is defined.Usually, described hydrolysis can
To carry out at a temperature of 40-90 DEG C, carry out preferably at a temperature of 60-80 DEG C.The time of described hydrolysis can basis
The temperature of hydrolysis is selected, and can be typically 2-4 hour.
According to the third aspect of the present invention, the invention provides the lithium ion battery negative prepared by said method is active
Material.
Intercalation modifying hectorite and geo are contained by negative active core-shell material prepared by the method for the present invention2, described intercalation modifying
The intercalator of hectorite is at least partially from described geo2, interlamellar spacing d of described intercalation modifying hectorite001For 1.2-5nm
(interlamellar spacing d for hectorite0011.2-10 times), preferably 1.9-3.5nm (interlamellar spacing d for hectorite0011.5-7
Times).
When also using cationic surfactant in the preparation process of the method for the present invention, the negative electrode active material of preparation
The interlamellar spacing of the intercalation modifying hectorite in material is generally d001For more than 1.5nm, preferably more than 2.5nm.
According to the fourth aspect of the present invention, the invention provides a kind of lithium ion battery negative material, this negative material
Including negative active core-shell material provided by the present invention and adhesive.Described negative active core-shell material and preparation method thereof is above
It is described in detail, here is omitted.
In the present invention, the species and content of described adhesive can be the conventional selection of this area.For example, negative pole is made
Adhesive can be Kynoar (pvdf), polytetrafluoroethylene (PTFE) (ptfe), butadiene-styrene rubber (sbr) and TPO emulsion
Etc. one or more of various modifications or non-modified adhesive.In general, the difference according to adhesive therefor species, with
On the basis of 100 weight portion negative active core-shell materials, the consumption of described adhesive can be 0.01-10 weight portion, preferably 0.02-8
Weight portion.
Described negative material can also contain conductive agent, to increase the electric conductivity of electrode, reduces the internal resistance of cell.Described conduction
Agent is not particularly limited, and can be the conventional negative pole conductive agent in this area, such as one of carbon black, nickel powder and copper powder or many
Kind.On the basis of 100 weight portion negative active core-shell materials, the consumption of described conductive agent can be 0-12 weight portion, preferably 2-10
Weight portion.
Each component in negative material can be mixed, thus obtaining described negative pole material using conventional various methods
Material.
According to the fifth aspect of the present invention, the invention provides a kind of lithium ion battery negative, this negative pole includes current collection
Body and coating and/or be filled in negative material on collector, wherein, the negative pole material that described negative material provides for the present invention
Material.The composition of described negative material has been carried out above describing, and here is omitted.
In the present invention, described collector can be collector used in traditional lithium-ion battery negative pole, for example, described
Collector can be one of stamped metal, metal forming, net metal, foamed metal.In order to improve described negative material
With the adhesion of collector, described collector preferably surface roughness is the collector of 0.1-1 micron.
Described negative pole can be prepared using the conventional method of this area.Specifically, by negative pole material provided by the present invention
Material is mixed with solvent, and by the pastel obtaining coating and/or is filled on described collector, is dried, rolls or do not roll, that is,
Can get described negative pole.
Described solvent can be sub- selected from n- methyl pyrrolidone, dimethylformamide, DEF, dimethyl
Sulfone, oxolane and one or more of water and alcohols.The consumption of solvent can make described pastel have viscosity and stream
Dynamic property, can be coated on described collector.In general, on the basis of 100 weight portion negative electrode active materials, described molten
The consumption of agent can be 50-150 weight portion, preferably 70-120 weight portion.
Described drying, the method for calendering and condition are known to those skilled in the art.For example, the temperature one of described drying
As be 100-150 DEG C.
According to the sixth aspect of the invention, the invention provides a kind of lithium ion battery, this battery includes pole piece and non-
Water electrolysis liquid, described pole piece and nonaqueous electrolytic solution are sealed in battery container, and described pole piece includes positive pole, negative pole and barrier film, its
In, the negative pole that described negative pole provides for the present invention.Described negative pole and preparation method thereof has been carried out above describing, herein not
Describe in detail again.
Because the improvements of the present invention pertain only to the negative pole of lithium ion battery, the lithium-ion electric therefore providing in the present invention
Chi Zhong, has no particular limits to the positive pole of battery, barrier film and nonaqueous electrolyte liquid, it is possible to use can make in lithium ion battery
All types of positive poles, barrier film and nonaqueous electrolytic solution.Those of ordinary skill in the art can be according to the religion of prior art
Lead, can easily select and prepare positive pole, barrier film and the nonaqueous electrolytic solution of lithium ion battery of the present invention, and by institute
Positive pole, the negative pole of the present invention, barrier film and the nonaqueous electrolytic solution stated is obtained the lithium ion battery of the present invention.
The composition of described positive pole is known to those skilled in the art.In general, positive pole include collector and coating and/
Or it is filled in positive electrode on collector, described positive electrode includes positive active material, conductive agent and adhesive.
The method according to the invention, the preparation method of described positive pole can be using various methods commonly used in the art, such as
Can include mixing positive active material, conductive agent and adhesive with solvent, coating and/or filling on the current collector, are dried,
Roll or do not roll, you can obtain described positive pole.
According to the present invention, described positive active material can adopt various positive active materials well known in the art, for example
licoo2、livpo4、licoalo2、limncoo2、licoxniymnzo2(x+y+z=1), limn2o4、linio2And lifexm1- xpo4One or more of (m is co, ni, mn, 0.8≤x≤1).In the present invention, the consumption of described positive active material is permissible
Conventional amount used for this area.
The present invention is not particularly limited for the conductive agent in described positive electrode, can lead for the conventional positive pole in this area
Electric agent, for example: in carbon black, graphite, acetylene black, carbon fiber, CNT, carbonyl nickel powder, copper powder, iron powder, zinc powder and aluminium powder
One or more.The consumption of the conductive agent in described positive electrode can be the conventional amount used of this area.Usually, with 100 weights
On the basis of amount part positive active material, the content of the conductive agent of positive pole can be 0.5-15 weight portion, preferably 1-10 weight portion.
Adhesive in described positive electrode can be various positive electrode binder commonly used in the art, for example: gather inclined difluoro
Ethene, polytetrafluoroethylene (PTFE), (fluorine-containing) polyacrylate, (fluorine-containing) polyurethane, (fluorine-containing) epoxy resin, butadiene-styrene rubber, poly- methyl
One or more of cellulose, poly- sodium carboxymethylcellulose pyce, hydroxypropyl methyl cellulose, POLYPROPYLENE GLYCOL and butadiene-styrene rubber (sbr).One
As for, according to the difference of adhesive therefor species, on the basis of 100 weight portion positive active materials, in described positive electrode
The content of adhesive can be 0.01-10 weight portion, preferably 0.02-7 weight portion
Preparing the solvent being used during positive pole can be various solvents commonly used in the art, for example, can be selected from n- methyl
In pyrrolidones, dimethylformamide, DEF, dimethyl sulfoxide (DMSO), oxolane and water and alcohol series solvent one
Plant or multiple.
The species of the collector in described positive pole is known to those skilled in the art, for example, can be selected from aluminium foil, copper
Paper tinsel, Punching steel strip.
Described barrier film is arranged between positive pole and negative pole, has electrical insulation capability and liquid retainability energy.Described barrier film can
With various barrier films used in lithium ion battery, such as polyolefin micro porous polyolefin membrane, polyethylene felt, glass mat or ultra-fine glass
Glass fibrous paper.The position of described barrier film, property and species are known to those skilled in the art.
Described nonaqueous electrolytic solution is the mixed solution of electrolyte lithium salt and nonaqueous solvents, and it is not particularly limited, permissible
Using the conventional nonaqueous electrolytic solution in this area.Such as electrolyte lithium salt is selected from lithium hexafluoro phosphate (lipf6), lithium perchlorate, tetrafluoro
One or more of lithium borate, hexafluoroarsenate lithium, lithium halide, chlorine lithium aluminate and fluorohydrocarbon base Sulfonic Lithium.Chain selected by nonaqueous solvents
Shape acid esters and ring-type acid esters mixed solution, wherein chain acid esters can be dimethyl carbonate (dmc), diethyl carbonate (dec), carbon
Sour methyl ethyl ester (emc), methyl propyl carbonate (mpc), dipropyl carbonate (dpc) and other fluorine-containing, sulfur-bearing or containing unsaturated bond
At least one in chain organosilane ester, ring-type acid esters can be ethylene carbonate (ec), propene carbonate (pc), carbonic acid Asia second
In alkene ester (vc), gamma-butyrolacton (γ-bl), sultone and other fluorine-containing, sulfur-bearing or the ring-type organosilane ester containing unsaturated bond
At least one.Generally, the injection rate of nonaqueous electrolytic solution is 1.5-5.5 gram/ampere-hour, concentration rubs for 0.1-2.0/liter.
The preparation method of the lithium ion battery providing according to the present invention, except described negative active core-shell material carries according to the present invention
For method preparation outside, other steps are known to those skilled in the art.In general, and born positive pole by membrane layer
Pole is wound around and separates formation electrode group, the electrode group obtaining and nonaqueous electrolytic solution is sealed in battery case, you can obtain the present invention
The lithium ion battery providing.The method for winding of the membrane layer between positive pole and negative pole is known to those skilled in the art,
Will not be described here.
The present invention will be more fully described by embodiment below.
Li in the negative active core-shell material of x-ray fluorescence spectrum method for measuring preparation is adopted in following examples and comparative example2O and
geo2Content, calculate the layer of the hectorite of hectorite and intercalation modifying using x-ray diffraction method and by Bragg equation
Spacing, measures the content of the cationic surfactant in negative active core-shell material using thermal weight loss method.
In following examples, hectorite is purchased from Guangzhou Bo Feng Chemical Industry Science Co., Ltd.
Embodiment 1
This embodiment is used for lithium ion battery anode active material that the present invention provides and preparation method thereof is described.
The hectorite of 5g is dissolved in 100ml deionized water, in 80 DEG C of water bath with thermostatic control dispersed with stirring 4h, obtains moisture and dissipate
Liquid.The ph value adjusting dispersion liquid with the naoh solution of 0.01mol/l is ph=11, at the uniform velocity drips 100ml in aqueous dispersions
(0.87mol)gecl4, drip 0.5 hour, and continue to react 2h；After the completion of reaction, solution is naturally cooled to room temperature, suction filtration,
It is washed to neutrality；It is vacuum dried 6h, thus obtaining the negative active core-shell material of the present invention at 200 DEG C of product.
The property of the negative active core-shell material of preparation is listed in Table 1.In Fig. 1, curve a is the hectorite as raw material
Xrd collection of illustrative plates, curve b is the xrd collection of illustrative plates of negative active core-shell material manufactured in the present embodiment.
Embodiment 2
This embodiment is used for lithium ion battery anode active material that the present invention provides and preparation method thereof is described.
The hectorite of 5g is dissolved in 100ml deionized water, in 80 DEG C of water bath with thermostatic control dispersed with stirring 3h, is subsequently adding
0.1g ctab continues dispersion 1h, obtains aqueous dispersions.The ph value adjusting aqueous dispersions with the naoh solution of 0.01mol/l is ph
=11, at the uniform velocity drip 100ml (0.87mol) gecl in aqueous dispersions4, drip 0.5h, and continue to react 2h；After the completion of reaction
Solution is naturally cooled to room temperature, suction filtration, is washed to neutrality；It is vacuum dried 6h, thus obtaining the negative of the present invention at 200 DEG C of product
Pole active material.
The property of the negative active core-shell material of preparation is listed in Table 1.In Fig. 1, curve c corresponds to the use of the present embodiment
The xrd collection of illustrative plates of the modified hectorite of ctab, curve d is the xrd collection of illustrative plates of negative active core-shell material manufactured in the present embodiment.
Embodiment 3
This embodiment is used for lithium ion battery anode active material that the present invention provides and preparation method thereof is described.
The hectorite of 5g is dissolved in 100ml deionized water, in 80 water bath with thermostatic control dispersed with stirring 3h, is subsequently adding 0.2g
Dodecyl benzyl dimethyl ammonium chloride continues dispersion 1h, obtains aqueous dispersions.Adjust moisture with the naoh solution of 0.01mol/l
The ph value of dispersion liquid is ph=11, at the uniform velocity drips 150ml (1.305mol) gecl in aqueous dispersions4, drip 0.5h, and continue anti-
Answer 2h；After the completion of reaction, solution is naturally cooled to room temperature, suction filtration, be washed to neutrality；It is vacuum dried 6h at 200 DEG C of product, from
And obtain the negative active core-shell material of the present invention.
The property of the negative active core-shell material of preparation is listed in Table 1.
Embodiment 4
This embodiment is used for lithium ion battery anode active material that the present invention provides and preparation method thereof is described.
The hectorite of 2.5g is dissolved in 50ml deionized water, in 80 DEG C of water bath with thermostatic control dispersed with stirring 3h, is subsequently adding
0.1g dodecyl benzyl dimethyl ammonium chloride continues dispersion 1h, obtains aqueous dispersions.Adjusted with the naoh solution of 0.01mol/l
The ph value of aqueous dispersions is ph=11, at the uniform velocity drips 40ml (0.348mol) gecl in aqueous dispersions4, drip 0.2h, and continue
Continuous reaction 2h；After the completion of reaction, solution is naturally cooled to room temperature, suction filtration, be washed to neutrality；It is vacuum dried at 200 DEG C of product
6h, thus obtain the negative active core-shell material of the present invention.
The property of the negative active core-shell material of preparation is listed in Table 1.
Embodiment 5
This embodiment is used for lithium ion battery anode active material that the present invention provides and preparation method thereof is described.
Cathode of lithium battery active material is prepared using technique same as Example 2, except that, the consumption of ctab is
0.01g, thus obtain the negative active core-shell material of the present invention.
The property of the negative active core-shell material of preparation is listed in Table 1.
Comparative example 1
With the naoh of 0.01mol/l, the ph value of the deionized water of 100ml is adjusted to 11, and the temperature of deionized water is risen to
80 DEG C, by 100ml (0.87mol) gecl4At the uniform velocity it is added drop-wise in deionized water, drips 0.5h, and continue to react 2h；Reaction completes
Afterwards solution is naturally cooled to room temperature, suction filtration, be washed to neutrality；Pulverize after vacuum drying 6h at 200 DEG C of product.After testing, really
It is set to geo2.
The property of the negative active core-shell material of preparation is listed in Table 1.
Comparative example 2
Prepare geo using with comparative example 1 identical method2, and the geo by preparation2Exist with embodiment 1 identical hectorite
25 DEG C directly mix in solid form, thus obtaining negative active core-shell material.
The property of the negative active core-shell material of preparation is listed in Table 1.
Comparative example 3
Cathode of lithium battery active material is prepared using method same as Example 2, except that, the consumption of ctab is
2g, thus obtain negative active core-shell material.
The property of the negative active core-shell material of preparation is listed in Table 1.
Table 1
Experimental example
The negative active core-shell material of embodiment 1-5 and comparative example 1-3 is made lithium ion battery using following methods.
(1) preparation of negative pole
The negative active core-shell material of embodiment 1-5 and comparative example 1-3 is made the negative pole of lithium battery, concretely comprise the following steps: respectively
By the negative active core-shell material of embodiment 1-5 and comparative example 1-3, super p conductive agent (commercially available from Shanghai chemical company of Hewlett-Packard),
(commercially available from Shanghai, Chang Guang enterprise is sent out for pvdf (commercially available from Aladdin reagent (Shanghai) Co., Ltd.) and carboxymethylcellulose calcium (cmc)
Exhibition Co., Ltd) uniformly mix in deionized water than 100:5:8:5 according to weight.Thickness be 50 microns Copper Foil on two-sided
Dressing, smears uniformly.At 120 DEG C dry, roll, rolling cut becomes negative plate, pole piece size be 3cm (length) × 1cm (wide) ×
0.2cm (thick).
(2) preparation of positive pole
6g pvdf is added in 20ml n- methyl pyrrolidone (nmp), after all dissolving, adds 6g super p
Conductive agent (commercially available from Shanghai chemical company of Hewlett-Packard) is simultaneously uniformly dispersed, then by 88g lifepo4 (commercially available from lg chemical company)
Powder is slowly added in above-mentioned mixed solution, and high-speed stirred is disperseed 2 hours, prepared anode sizing agent.It it is 50 microns in thickness
Two-sided dressing on aluminium foil, smears uniformly.Dry at 140 DEG C, roll, rolling cut becomes positive plate, pole piece size is 3cm (length) × 1cm
(wide) × 0.2cm (thick).
(3) assembling of battery
Above-mentioned positive and negative electrode and polypropylene screen (commercially available from Japanese asahi company) are wound into a square lithium-ion electricity
The pole piece in pond, subsequently by lipf6By the concentration of 1 mol/L be dissolved in vinyl carbonate (ec), diethyl carbonate (dec) and
In the mixed solvent of dimethyl carbonate (dmc) (ec:dec:dmc=1:1:0.5 (weight ratio)), thus obtaining non-aqueous solution electrolysis
Liquid.By the nonaqueous electrolytic solution obtaining, in the amount injection battery case of 5.2g/ah, to seal, to make lithium rechargeable battery.
The negative active core-shell material of embodiment 1-5 and comparative example 1-3 is made lithium ion battery and is designated as c1-c5 and d1- respectively
d3.
Test case
The test of cycle performance of lithium ion battery
Lithium ion battery c1-c5 and d1-d3 is carried out respectively under the conditions of 0.2c charge-discharge magnification charge-discharge test.Fig. 2
Respectively show the circulation performance curve distribution of lithium ion battery c1, c2 and d1 to Fig. 4.
The cycle performance of lithium ion battery c1-c5, d1-d3 of preparation is as shown in table 2.
Table 2
Can find out respectively from table 2 and Fig. 2-4, in the negative material of the present invention, combine intercalation modifying hectorite conduct
Material modified, the cycle performance of battery can be significantly improved.Can be seen that the side of the present invention by the data of embodiment 1 and comparative example 2
The negative active core-shell material ratio of method preparation is simply by hectorite and geo2The prepared negative active core-shell material of mixing has preferably
Cycle performance.
Claims (18)
1. a kind of lithium ion battery anode active material, this negative active core-shell material contains intercalation modifying hectorite and geo2, its feature
It is, the intercalator of described intercalation modifying hectorite is at least partially from described geo2, the layer of described intercalation modifying hectorite
Spacing d001For 1.2-5nm.
2. negative active core-shell material according to claim 1, wherein, with li2The described intercalation modifying hectorite of o meter and geo2
Mass ratio be 1:2.4-9.5.
3. negative active core-shell material according to claim 1 and 2, wherein, described negative active core-shell material also contains at least one
Cationic surfactant, the intercalator part of described intercalation modifying hectorite comes from described cationic surfactant, institute
State interlamellar spacing d of intercalation modifying hectorite001For more than 1.5nm.
4. negative active core-shell material according to claim 3, wherein, on the basis of the gross mass of described negative active core-shell material,
The content of described cationic surfactant is 0.01-1 weight %.
5. negative active core-shell material according to claim 3, wherein, described cationic surfactant is cetyl front three
In base ammonium bromide, dodecyl benzyl dimethyl ammonium chloride, double octyl ditallowdimethyl ammonium bromide and adamantane mono-quaternaries one
Plant or multiple.
6. a kind of preparation method of lithium ion battery anode active material, the method includes: under the conditions of hydrolysis, will at least
A kind of compound is contacted with the aqueous dispersions containing hectorite, and described compound can form geo under the conditions of hydrolysis2.
7. method according to claim 6, wherein, the method obtaining described aqueous dispersions includes: hectorite is mixed with water
Close.
8. method according to claim 7, wherein, the method obtaining described aqueous dispersions is also included, by hectorite and water
It is mixed to get mixture, more described mixture is contacted with least one cationic surfactant, wherein, described cation form
The consumption of face activating agent makes in the negative active core-shell material finally prepared, and the content of cationic surfactant is 0.01-1 weight
Amount %.
9. method according to claim 8, wherein, the condition that described mixture is contacted with described cationic surfactant
Including: temperature is 60-80 DEG C, and the time is 0.5-1.5 hour.
10. method according to claim 8 or claim 9, wherein, described cationic surfactant is cetyl trimethyl bromine
Change one of ammonium, dodecyl benzyl dimethyl ammonium chloride, double octyl ditallowdimethyl ammonium bromide and adamantane mono-quaternaries or
Multiple.
11. methods according to claim 6, wherein, before described aqueous dispersions are contacted with described compound, the method
Also include for the ph value of described aqueous dispersions being adjusted to 10-11.
12. methods according to claim 6, wherein, the consumption of described compound makes the negative electrode active material finally prepared
With li in material2The intercalation modifying hectorite of o meter and geo2Mass ratio be 1:
2.4-9.5.
13. methods according to any one in claim 6,11 and 12, wherein, described compound is gex4, x be cl or
br.
14. methods according to claim 6, wherein, described hydrolysis condition includes: temperature is 60-80 DEG C, with timely
Between be 2-4h.
The lithium ion battery anode active material of the 15. method preparations described in any one in claim 6-14.
A kind of 16. lithium ion battery negative materials, this negative material include negative active core-shell material and adhesive it is characterised in that
Described negative active core-shell material is the negative active core-shell material in claim 1-5 and 15 described in any one.
A kind of 17. lithium ion battery negatives, this negative pole includes collector and coating and/or is filled in the negative pole material on collector
Material is it is characterised in that described negative material is the negative material described in claim 16.
A kind of 18. lithium ion batteries, this battery includes pole piece and nonaqueous electrolytic solution, and described pole piece and nonaqueous electrolytic solution are sealed in electricity
In the housing of pond, described pole piece includes positive pole, negative pole and barrier film it is characterised in that described negative pole is negative described in claim 17
Pole.
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